Vinyl chloride plastic compositions and certain plasticizers therefor

ABSTRACT

THE INVENTION PROVIDES AN N-ALKYL-N-3-ETHOXYPROPYLOLEAMIDE, WHEREIN THE ALKYL GROUP CONTAINS 1-4 CARBON ATOMS, WHICH IS USEFUL AS A PLASTICIZER FOR VINYL CHLORIDE RESINS.

United States Patent 3,787,457 VINYL CHLORIDE PLASTIC COMPOSITIONS ANDCERTAIN PLASTICIZERS THEREFOR Robert R. Mod, 4550 Arthur Drive 70127;Frank C. Magne, 2330 Franklin Ave. 70117; and Evald L. Skau, 6473Memphis St. 70124, all of New Orleans, L

US. Cl. 260-404 1 Claim ABSTRACT OF THE DISCLOSURE The inventionprovides an N-alkyl-N-S-ethoxypropyloleamide, wherein the alkyl groupcontains 1-4 carbon atoms, which is useful as a plasticizer for vinylchloride resins.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedState Government, with the power to grant sublicenes for such purposes,is hereby granted to the Government of the United States of America.

This application is a division of application Ser. No. 141,361, filedMay 7, 1971, which, in turn, is a division of application Ser. No.876,556, filed Nov. 13, 1969, now US. Pat. No. 3,644,478, which, inturn, is a division of application Ser. No. 683,060, filed Oct. 12,1967, now abandoned, and which, in turn, is a division of applicationSer. No. 529,652, filed Feb. 24, 1966, now U.S. Pat. No. 3,403,126.

This invention relates to certain compounds which are N-acyl derivativesof symmetrical or asymmetrical secondary amines, to some unique mixturesof the same, and to plastic compositions, the plasticizer component ofwhich is at least one of the compounds or unique mixtures that are thesubject of this invention. More particularly, this invention relates toN,N-disubstituted longchain aliphatic amides the acyl component of whichif saturated is an alkanoic acyl containing from to 18 carbon atoms, andif unsaturated is a monoalkenoic acyl containing from 18 to 22 carbonatoms, the amide nitrogen in all cases being the nitrogen atom of asymmetrical or asymmetrical s condary, acyclic or alicyclic amine, saidsecondary amine being a substituted or unsubstituted acyclic oralicyclic amine.

Specifically this invention relates to symmetrical and asymmetricalN,N-dialkyl amide plasticizers wherein the total number of carbon atomsin the two alkyl groups is from 5 to about 14; to asymmetricalN,N-disubstituted amide plasticizers wherein one of the substituents onthe amide nitrogen is an alkyl group containing from 1 to 4 carbon atomsand the other is a radical chosen from the group consisting of allyl,2,3-epoxypropyl, an alicyclic hydrocarbon radical containing from 5 to12 carbon atoms, benzyl, furfuryl, tetrahydrofurfuryl, 2 acetoxyethyl,2- methoxyethyl, 2-ethoxyethyl, 2-ethoxypropyl and Z-cyanoethyl; and toasymmetrical N,N-disubstituted amide plasticizers wherein thesubstituents on the amide nitrogen are selected from the group benzyl,cyclohexyl, 2-acetoxyethyl, and 2-cyanoethyl. This invention alsorelates to certain other new amide plasticizers wherein the acylcomponent is derived from epoxyalkanoic or epoxyalkenoic acids, frommonoalkyl esters of pinic acid, from branched chain or neo acids, orfrom long-chain acyl derivatives of short-chain hydroxy acids.

More specifically this invention relates to compounds and mixtures ofcompounds that are good, compatible, solvent-type plasticizers for vinylchloride resins; moreover the compounds and mixtures of this inventionare efiicient, primary, solvent-type plasticizers which can be made fromlow-price fatty acids and which exhibit good compatibility with andimpart not only low volatility loss, resistance to microbial action,excellent low-temperature properties (low brittle points), and stabilityagainst northern light exposure, but also excellent thermal stabilityand antistatic properties to vinyl chloride polymer and copolymerresins.

A polyvinyl chloride resin, being a hydrophobic resin, differs fromhydrophilic resins such as cellulose esters, cellulose acetate,cellulose nitrate, and polyvinyl acetal resins in two importantrespects; (1) It tends to develop static charges on its surface due tofrictional forces during manufacture or in everyday use of the plasticproducts. This results in (a) the attraction of dust and lint to theplastic surface, (b) the tendency of one surface or film to adhere toanother, and (c) in general, interference with efiicient manufacture andwith consumer acceptance of the finished product. For example, a staticcharge may be developed by the friction of ones clothing on anautomobile plastic seat cover and may even result in a slight butunpleasant spark or shock when the passenger grounds himself or alights.(2) Polyvinyl chloride tends to undergo decomposition on extendedexposure to even moderately elevated temperatures, resulting indarkening and development of discoloration. Different plasticizersaffect the stability of the polyvinyl chloride to different degrees,some impair and others improve the thermal stability.

Although antistatic properties may be imparted to a surface, at leasttemporarily, by spraying on or coating with a film of antistatic agent,the antistatic properties imparted have limited permanence and are lostas the film is worn or washed away. It is much more advantageous, bothfrom the point of view of permanence and of eliminating need for thespraying or coating operation, to use an antistatic agent which is acompatible plasticizer, which can be used as the sole plasticizer, andwhich when so incorporated in the plastic compositions still retains andexhibits its antistatic properties.

It is known that N,N-dimethyl-oleamide is an eflicient, primary,low-temperature' plasticizer for polyvinyl chloride resins. Thiscompound is also known to possess antistatic properties. We havediscovered, in addition, that when N,N-dimethyl-oleamide is used as theplasticizer in polyvinyl chloride resin the plasticized stock also hasexcellent antistatic properties. However, polyvinyl chloride resinplasticized with N,N-dimethyl-olearnide exhibits extremely poor thermalstability and therefore it cannot be used for commercial applicationsinvolving exposure. to even moderately elevated temperatures, such forexample, as would be encountered in a closed automobile in summerweather.

It was disclosed by Dazzi in US. Pat 2,875,218 that the N,N,N',-tetramethyl and N,N,N',N'-tetra-n-butyl diamides of dimeric linoleicacid are plasticizers for polyvinyl chloride resins. We have found thatN,N,N',N'-tetran-bntyl diamide of dimeric linoleic acid has excellentantistatic properties. However, polyvinyl chloride resin plasticizedwith this diamide has no antistatic properties and has the addeddisadvantage that it exhibits poor thermal stability.

We have made the surprising discovery that when certain of the compoundsof this invention are used as plasticizers for polyvinyl chloride resinsthe plasticized resin possesses both excellent antistatic properties andexcellent thermal stability.

The terms vinyl type resin and vinyl chloride resin are used throughoutthis specification and claims to refer to homopolymers and copolymers ofmonomers containing vinyl chloride in a predominant proportion byweight. Terms such as compatible, good compatibility, and compatibleplasticizer in reference to the plasticizers which are the subject ofthis invention are used throughout the specification to refer toplasticizers that show no sign of exudation, migration to the surface,for at least 30 days when the plasticizers are present in the resin inproportion of about 70 parts by weight of plasticizers to 100 parts byweight of resin.

If a resin is plasticized with a compound with which it has only limitedcompatibility, the plasticizer soon exudes or migrates to the surfaceunless the plasticizer is used either in a limited amount or is used inconjunction with a mutual solvent (a compatible auxiliary plasticizer)to obtain adequate compatibility.

It is known in the art that compounds similar to some of those which arethe subject of this invention exhibit reasonably good compatibility forhydrophilic-type resins but in order to obtain adequate flexibility mustbe employed together with a secondary or an auxiliary plasticizer asthose shown, for example, in US. Patent No. 2,339,056.

It would be expected from the recognized compatibility of certaincompounds related to types herein described with polyvinyl acetals(hydrophilic-type resins,) that these compounds would be quiteincompatible with polymers of the vinyl chloride type. Certain of theparticular compounds and compound mixtures herein described are, however, compatible as primary plasticizers with vinyl chloride resins and,as we note above, they are compatible with the hydrophilic-type resinsas well.

Not only are the particular compounds and mixtures of compounds hereindescribed compatible vinyl-type resin plasticizers, but the instantinvention is considerably broader in that it also contemplates the useof compatible binary, ternary, or multiple component mixtures of N,N-disubstituted amides of mixed saturated, monounsaturated, andpolyunsaturated acids such as can be derived from animal, fish, orvegetable fat and oils such as tallows, white greases, menhaden oil,cottonseed oil, soybean oil, rapeseed oil, safflower oil, Crambeabyssinica seed oil, jojoba oil, parsley seed oil, Limnanthes douglasiiseed oil, palm oil, Vernonia anthelmintica seed oil, castor oil, foots,or from tall oil acids or rosin acids, and other seed oils.

The N-acyl derivatives of this invention decrease in their degree ofcompatibility as the alkyl portion of the acyl group (if saturated}increases in chain length beyond 15 carbon atoms and they areincompatible when the chain length is 17 or more carbon atoms. Ingeneral, the compatibility of a mixture of these N-acyl derivatives ofsecondary amines containing a considerable proportion of these lesscompatible or incompatible N-acyl derivatives can be improved by mixingwith a compatible plasticizer or by reducing the proportion of theincompatible saturated constituents by such procedures as fractionaldistillation or fractional crystallization either before or after theamidation step in the preparation of the N-acyl secondary amine mixture.Similarly, the N-acyl derivatives of this invention decrease in theirdegree of compatibility as the alkyl portion of the acyl group of theN-acyl derivative (if unsaturated) increases in unsaturation beyondmonounsaturation. In general, the compatibility of such apolyunsaturated derivative or of a mixture of N-acyl secondary aminessome of which contain such a polyunsaturated acyl can be increased bymixing with a suitable amount of a compatible plasticizer or bydecreasing the proportion of the polyunsaturated constituent either byphysical means, such as fractionation, or by chemical means such asselective hydrogenation, cyanoethylation, halogenation, epoxidation,formylation, maleination, or the like either before or after theamidation step in the preparation of the N-acyl secondary amine orN-mixedacyl secondary amine. The specific component ratio of compatiblecompositions can be established according to the scheme set forth in ourcopending application Serial No. 334,685 filed December 10, 1963, forexample.

The preferred N,N-dial-kylamides of this invention are those in whicheach of the alkyl substituents on the amide nitrogen contains two ormore carbon atoms and the total number of carbons in the two alkylgroups is from 6 to 14. The preferred asymmetrically N,N-disubstitutedamides of this invention having one alkyl substituent on the amidenitrogen are those in which the alkyl group contains two or more carbonatoms and the total number of carbons in the two substituents is lessthan about 14.

The compounds that are the subject of this invention are convenientlyprepared by reacting the appropriate secondary amine with theappropriate acid, or corresponding acid chloride. In any event, methodsfor preparing compounds such as those described herein are well known tothose skilled in the art of fatty acid chemistry. The details ofindividual preparations are listed in the following operating examples.These examples are set forth by Way of illustration and it will beunderstood that the invention is not to be construed as limited to thesecompounds or by the details therein. Analyses are in weight percent.

EXAMPLE 1 N,N-di-n-propyl-oleamide 20 grams (0.20 mole) ofdi-n-propylamine and 15.6 grams (0.20 mole) of pyridine were dissolvedin ml. of benzene and 59.5 grams (0.20 mole) of oleoyl chloride wereadded dropwise with stirring. After stirring for an additional hour thereaction was filtered, washed successively with dilute hydrochloric acidand water, and dried over anhydrous sodium sulfate. Free acid wasremoved by percolating the benzene solution through a column ofactivated alumina and eluting the amide with a 1:1 ethanol-benzenemixture. The solvent was then removed by stripping under reducedpressure. Analysis of the product, N,N-di-n-propyl-oleamide: percent78.82 (theory 78.86); percent H, 12.98 (theory 12.98); percent N, 3.64(theory 3.63).

EXAMPLE 2 N,N-di-isopropyl-ole amide This compound was prepared by theprocedure of Example 1, from 11.9 grams (0.12 mole) of diisopropylamine,35 grams (0.12 mole) of oleoyl chloride, and 9.2 grams (0.12 mole) ofpyridine. Analysis of the product, N,N-di-isopropyl-oleamide: percent C,76.87 (theory 78.76); percent H, 12.69 (theory 12.96); percent N, 3.56(theory 3.83).

EXAMPLE 3 N ,N,di n-butyl-oleamide A mixture of 27.5 grams (0.21 mole)of di-n-butylamine, 40 grams (0.14 mole) of oleic acid, and 20milliliters of benzene was refluxed in an apparatus equipped with aDean-Stark trap until the evolution of water ceased. The mixture wasdiluted with 150 ml. of commercial hexane, washed successively withdilute hydrochloric acid and Water, and dried over anhydrous sodiumsulfate. Free acid was removed by percolating the hexane solutionthrough a column of activated alumina, and eluting the amide with 1:1hexane-ethanol mixture. The solvent was removed by stripping underreduced pressure. Analysis of the product, N,N-di-n-butyl-oleamide:percent C, 78.94- (theory 79.25); percent H, 13.16 (theory 13.06);percent N, 3.44 (theory 3.56).

EXAMPLE 4 N,N-di-sec-butyl-oleamide This compound was prepared by theprocedure of Example 1 from 20 grams (0.15 mole) of di-sec iwutylamine,46.6 grams (0.15 mole) of oleoyl chloridt and 1,2 3

grams (0.15 mole) of pyridine. Analysis of the productN,N-di-sec-butyl-oleamide: percent C, 79.04 (theory 79.27); percent H,13.38 (theory 13.06); percent N, 2.94 (theory 3.56).

EXAMPLE 5 N ,N-di-isobutyl-oleamide This compound was prepared by theprocedure of Example 1, from 15 grams (0.12 mole) of diisobutylamine, 35grams (0.12 mole) of oleoyl chloride and 9.2 grams (0.12) of pyridine.Analysis of the product, N,N-di-isobutyl-oleamide: percent C, 78.78(theory 79.25); percent H, 13.10 (theory 13.06); percent N, 3.56 (theory3.56).

EXAMPLE 6 N,N-di-n-amyl-oleamide This compound was prepared by procedureof Example 1, from 18.3 grams (0.12 mole) of di-n-amylamine, 35 grams(0.12 mole) of oleoyl chloride and 9.3 grams (0.12 mole) of pyridine.Analysis of the product, N,N-di-namyl-oleamide: percent C, 79.68 (theory79.81); percent H, 13.28 (theory 13.15); percent N, 3.29 (theory 3.32).

EXAMPLE 7 N,N-di-isoamyl-oleamide This compound was prepared by theprocedure of Example 1, from 19 grams (0.12 mole) of di-isoamylamine,38.3 grams (0.12 mole) of oleoyl chloride and 9.6 grams (0.12 mole) ofpyridine. Analysis of the product, N,N-diisoamyl-oleamide: percent C,78.90 (theory (78.78); percent H, 13.14 (theory 13.15); percent N, 3.25(theory 3.32).

EXAMPLE 8 N,N-di-2-amyl-oleamide This compound was prepared by theprocedure of Example 1, from 19 grams (0.12 mole) of di-2-amylamine,38.3 grams (0.12 mole) of oleoyl chloride and 9.6 grams (0.12 mole) ofpyridine. Analysis of the product, N,N-di- Z-amyl-oleamide: percent C,79.34 (theory 79.69); percent H, 12.84 (theory 13.14); percent N, 3.46(theory 3.32).

EXAMPLE 9 N,N-di-n-hexyl-oleamide N,N-di-n-heptyl-oleamide Thi compoundwas prepared by the procedure of Example 1 from 21.3 grams (0.10 mole)of di-n-heptylamine, 30 grams (0.10 mole) of pyridine. Analysis of theproduct, N,N-di-n-heptyl-oleamide: percent C, 80.03 (theory 80.36);percent H, 13.34 (theory 13.31); percent N, 2.86 (theory 2.93).

EXAMPLE 11 N,N-di-n-octyl-olearnide This compound was prepared by theprocedure of Example 1, from 24.1 grams (0.10 mole) of di-n-octylamine,30 grams (0.10 mole) of oleoyl chloride, and 7.9 grams (0.10 mole) ofpyridine. Analysis of the product, N,N-di-n-octyl-oleamide: percent C,80.58 (theory 80.65); percent H, 13.39 (theory 13.35); percent N, 2.72(theory 2.77).

6 EXAMPLE 12 N,N-di-2-ethylhexyl-oleamide This compound was prepared bythe procedure of Example 1, from 24.1 grams (0.10 mole) ofdi-Z-ethylhexylamine, 30 grams (0.10 mole) of oleoyl chloride and 7.9grams (0.10 mole) of pyridine. Analysis of the product, N,N-di 2ethylhexyl-oleamide: percent C, 79.80 (theory 80.65 percent H, 13.25(theory 13.24); percent N, 2.90 (theory 2.77).

EXAMPLE 13 N,N-di-n-decyl-oleamide This compound was prepared by theprocedure of Example 1, from 22.7 grams (0.08 mole) of di-n-decylamine,23 grams (0.08 mole) of oleoyl chloride, and 6.1 grams (0.08 mole) ofpyridine. Analysis of the product, N,N-di-n-decyl oleamide: percent C,81.01 (theory 81.13); percent H, 13.37 (theory 13.45); percent N, 2.43(theory 2.49).

EXAMPLE 14 N,N-di-n-butyl 2-ethylhexanarnide This compound was preparedby the procedure of Example 2, from 27.8 grams (0.22 mole) ofdi-n-butylamine, 35 grams (0.22 mole) of 2-ethylhexanoyl chloride, and17.0 grams (0.22 mole) of pyridine. Analysis of the product, N,N di nbutyl 2 ethylhexanamide: percent C, 74.97 (theory 75.16); percent H,12.48 (theory 12.92); percent N, 5.15 (theory 5.48).

EXAMPLE 15 N,N-di-n-butyl-neotridecanamide This compound was prepared bythe procedure of Example 1, from 26.1 grams (0.20 mole) ofdi-n-butylamine, 16 grams (0.20 mole) of pyridine and 40 grams (0.20mole) of neodecanoyl chloride. Analysis of the product, N,N di n butylneodecanamide: percent C, 76.10 (theory 76.19); percent H, 13.25 (theory13.05); percent N, 4.90 (theory 4.94).

EXAMPLE 16 N,N-di-n-butyl-neodecanamide This compound was prepared bythe procedure of Example 1, from 22.2 grams (0.17 mole) ofdi-n-butylamine, 40 grams (0.17 mole) of neotridecanoyl chloride and13.6 grams (0.17 mole) of pyridine. Analysis of the product,N,N-di-n-butyl neotridecanamide: percent C, 77.27 (theory 77.47);Percent H, 13.26 (theory 13.22); percent N, 4.29 (theory 4.31).

EXAMPLE l7 N,N-di-n-butyl-palmitamide This compound was prepared by theprocedure of Example 3, from 30.2 grams (0.23 mole) of di-n butylamineand 40 grams (0.16 mole) of palmitic acid, Analysis of the product,N,N-di-n-butyl-palmitamidez percent C, 78.75 (theory 78.33); percent H,13.72 (theory 13.43); percent N, 4.04 (theory 3.81).

EXAMPLE 18 N,N-di-n-butyl-stearamide This compound Was prepared by theprocedure of Example 3, from 28 grams (0.22 mole) of di-n-butylamine and40 grams (0.14 mole) of palmitic acid. Analysis of the product,N,N-di-n-butyl-palmitamide: percent C, 78.86 (theory 78.85); percent H,13.51 (theory 13.50); percent N, 3.49 (theory 3.54).

EXAMPLE 19 N,N-di-n-butyl-erucamide This compound was prepared by theprocedure of Example 3, from 22.8 grams (0.18 mole) of di-n-butylamine,and 40 grams (0.12 mole) of erucic acid. Analysis of the product,N,N-di-n-butyl-erucamide: percent C, 79.99 (theory 80.03); percent H,13.11 (theory 13.22); percent N, 3.07 (theory 3.09).

EXAMPLE 20 N,N-di-n-butyl-epoxystearamide This compound was prepared byepoxidation of N,N- di-n-butyl-oleamide, using meta-chloroperbenzoicacid. The product, N,N-di-n butyl-epoxystearamide had an oxirane oxygencontent of 3.43%.

EXAMPLE 21 N,N-di-n-butyl-linoleamide This compound was prepared by theprocedure of Example 3, from 27.7 grams (0.21 mole) of di-n-butylamineand 40 grams (0.14 mole) of linoleic acid. Analysis of the product,N,N-di-n-butyl-linoleamide: percent C, 79.19 (theory 79.65); percent H,12.71 (theory 12.61); percent N, 3.45 (theory 3.58).

EXAMPLE 22 N,N-di-n-butyl-ricinoleamide 50 grams (0.16 mole) of methylricinoleate and 41.4 grams (0.32 mole) of di-n-butylamine were refluxedat a temperature such that the methyl alcohol was removed without thedistillation of the di-n-butylamine. The reaction was continued for 36hours after which the product was cooled, dissolved in Skellysolve B,neutralized with dilute aqueous HCl and then water washed. The mixturewas dried over anhydrous sodium sulfate, filtered and then strippedunder reduced pressure. The impure amide was then distilled under 1 mm.pressure. Analysis of the product, N,N-di-n-butyl-ricinoleamide: percentC, 76.32 (theory 76.15); percent H, 12.62 (theory 12.45); percent N,3.34 (theory 3.42).

EXAMPLE 23 N,N-di-n-butyl-naphthenamide This compound was prepared bythe procedure of Example 3 from 35.7 grams (0.28 mole) of di-n-butylamine and 40 grams (0.18) mole of naphthenic acid (neut. equiv. 217).The product, N,N-di-n-butyl-naphthenamide, had a nitrogen content of4.20%.

EXAMPLE 24 N,N,N',N-tetra-n-butyl diamide of dimeric linoleic acid Thiscompound was prepared by the procedure of Example 3, from 27.7 grams(0.21 mole) of di-n-butylamine and 40 grams (0.071 mole) of dimericlinoleic acid. The product, the N,N,N',N'-tetra-n-butyl diamide ofdimeric linoleic acid, had a nitrogen content of 3.55% (theory 3.58%).

EXAMPLE 25 Ethyl-2,2-dimethyl-3 (di-n-butylamino)carbonylcyclobutaneacetate This compound was prepared by the procedureof Example 1, from 22.2 grams (0.17 mole) of di-n-butylamine, 40 grams(0.17 mole) of ethyl-2,2-dimethyl-3- chlorcarbonylcyclobutaneacetate,and 13.6 grams (0.17 mole) of pyridine. Analysis of the product,ethyl-2,2-dimethyl 3(di n-butylamino)carbonylcyclobutaneacetate: percentC, 70.11 (theory 70.09); percent H, 10.90 (theory 11.15); percent N,4.14 (theory 4.30).

EXAMPLE 26 N,N,-di-n-buty1 amide of cottonseed fatty acids This compoundwas prepared by the procedure of Example 3, from 24.6 grams (0.19 mole)of di-n-butylamine and 40 grams (0.15 mole) of cottonseed oil fattyacids. The product, the N,N-di-n-butyl amide of cottonseed fatty acids,had a nitrogen content of 3.26%.

8 EXAMPLE 27 N,N-di-n-butyl amide of selectively hydrogenated cottonseedfatty acids EXAMPLE 28 N,N-di-n-butyl amide of rapeseed fatty acids Thiscompound was prepared by the procedure of Example 3, from 31.9 grams(0.25 mole) of di-n-butylamine and 50 grams (0.16 moles) of rapeseed oilfatty acids. The product, the N,N-di-n-butyl amide of rapcseed fattyacids, had a nitrogen content of 3.08%.

EXAMPLE 29 N,N-di-n-butyl amide of Limnanthes douglasii fatty acids Thiscompound was prepared by the procedure of Example 3, from 24.3 grams(0.19 mole) of di-n-butylamine and 40 grams (0.13 mole) of Limnanthesdouglasii seed fatty acids. The product, N,N-di-n-buty1 amide ofLimnanthes douglasii fatty acids, had a nitrogen content of 3.23%.

EXAMPLE 30 N,N-di-n-butyl amide of animal acids This compound wasprepared by the procedure of Example 3, from 27.8 grams (0.22 mole) ofdi-n-butylamine, and 40 grams (0.15 mole) of animal acids. (The animalacids" consisted of a mixture of fatty acids, having the followingcomposition: 2% myristic, 26% palmitic, 16% stearic, 48% oleic, and 8%linoleic acids). The product, N,N-di-n-butyl amide of animal acids, hada nitrogen content of 3.25%.

EXAMPLE 31 N,N-di-n-buty1 amide of parsley seed fatty acids Thiscompound was prepared by the procedure of Example 3, from 30.5 grams(0.24 mole) of di-n-butylamine and 50 grams (0.16 mole) of parsley seedoil fatty acids. The product, N,N-di-n-butyl amide of parsley seed fattyacids, had a nitrogen content of 3.08%.

EXAMPLE 32 N-methyl-N-propyl-oleamide This compound was prepared by theprocedure of Example 1, from 15 grams (0.20 mole) ofN-methylpropylamine, 61.8 grams (0.21 mole) of oleoyl chloride and 16.3grams (0.21 mole) of pyridine. Analysis of the product,N-methyl-N-propyl-oleamide2 percent C, 77.57 (theory 78.23); percent H,12.91 (theory 13.93); percent N, 3.97 (theory 4.15).

EXAMPLE 33 N-methyl-N-n-butyl-oleamide This compound was prepared by theprocedure of Example 1, from 11.6 grams (0.13 mole) ofN-methylbutylamine, 10.5 grams (0.13 mole) of pyridine and 40 grams(0.13 mole) of oleoyl chloride. Analysis of the product,N-rnethyl-N-n-butyl-oleamide: percent C, 77.67 (theory 78.75); percentH, 12.88 (theory 12.94); percent N, 3.88 (theory 4.00).

EXAMPLE 34 N-methyl-N-n-amyl-oleamide This compound Was prepared by theprocedure of Example 1, from 15 grams (0.15 mole) of N-methylarnylamine,44.6 grams (0.15 mole) of oleoyl chloride, and

' 11.7 grams (0.15 mole) of pyridine. Analysis of the product,N-methyl-N-n-amyl-oleamide: percent C, 78.76 (theory 78.80); percent H,12.84 (theory 12.86); percent N, 3.86 (theory 3.83).

EXAMPLE 35 N-methyl-N-n-hexyl-oleamide This compound was prepared by theprocedure of Example 1, from 20 grams (0.17 mole) ofN-methylbhexylamine, 52.3 grams (0.17 mole) of oleoyl chloride and 13.8grams (0.17 mole) pyridine. Analysis of the product,N-methyl-N-n-hexyl-oleamide: percent C, 78.99 (theory 79.06); percent H,13.33 (theory 12.91); percent N, 3.52 (theory 3.69).

EXAMPLE 36 N-methyl-N-n-octyl-oleamide This compound was prepared by theprocedure of Example 1, from 20 grams (0.14 mole) of N-methyloctylamine,42.1 grams (0.14 mole) of oleoyl chloride, 11.1 grams (0.14 mole) ofpyridine. Analysis of the product, N-methyl-N-n-octyl-oleamide: percentC, 78.86 (theory 79.52); percent H, 13.03 (theory 13.01); percent N,3.35 (theory 3.44).

EXAMPLE 37 N-rnethyl-N-n-dodecyl-oleamide This compound was prepared bythe procedure of EX- ample 1, from 20 grams (0.10 mole) ofN-methyldodecylamine, 33.1 grams (0.11 mole) of oleoyl chloride and 8.0grams (0.10 mole) of pyridine. Analysis of the product,N-methyl-N-n-dodecyl-oleamide: percent C, 80.38 (theory 80.44); percentH, 13.39 (theory 13.19); percent N, 2.95 (theory 3.03).

EXAMPLE 38 N-methyl-N-allyl-oleamide This compound was prepared by theprocedure of Example 1, from grams (0.21 mole) of N-methylallylamine,63.5 grams (0.21 mole) of oleoyl chloride, and 16.7 grams (0.21 mole) ofpyridine. Analysis of the product, N-methyl-N-allyl-oleamide: percent C,77.68 (theory 78.70); percent H, 12.13 (theory 12.22); percent N, 4.21(theory 4.18).

EXAMPLE 39 N-butyl-N-n-dodecyl-oleamide This compound was prepared bythe procedure of Example 1, from grams (0.08 mole) ofN-butyldodecylamine, grams (0.08 mole) of oleoyl chloride and 6.6 grams(.08 mole) of pyridine. Analysis of the product, N-butyl-N-n-dodecyl-oleamide: percent C, 80.55 (theory 82.26); percent H,13.53 (theory 13.61); percent N, 2.88 (theory 2.82).

EXAMPLE 40 N-butyl-N-propyl-oleamide This compound was prepared by theprocedure of Example 1, from 20 grams (0.18 mole) ofN-butyl-N-propylamine, 54.8 grams (0.18 mole) of oleoyl chloride and13.7 grams (0.18 mole) of pyridine. Analysis of the productN-butyl-N-propyl-olea-mide: percent C, 78.59 (theory 79.16); percent H,13.20 (theory 13.03); percent N, 3.69 (theory 3.69).

EXAMPLE 41 N-butyl-N-n-amyl-oleamide This compound was prepared by theprocedure of Example 1, from 20 grams (0.14 mole) ofN-butyl-N-amylamine, 44 grams 0.14 mole) of oleoyl chloride, and 11.1grams (0.14 mole) of pyridine. Analysis of the productN-butyl-N-n-amyl-oleamide: percent C, 79.68 (theory 82,52); percent H,12.96 (theory 13.11); percent N, 3.39

(theory 3.44).

1 0 EXAMPLE 42 N-methyl-N-cyclopentyl-oleamide This compound wasprepared by the procedure of Example 1, from 15 grams (0.15 mole) ofN-methylcyclopentylamine, 45.5 grams (0.15 mole) of oleoyl chloride, and12 grams (0.15 mole) of pyridine. Analysis of the product,N-methyl-N-cyclopentyloleamide: percent C, 77.77 (theory 79.54); percentH, 12.29 (theory 12.48); percent N, 3.84 (theory 3.86).

EXAMPLE 43 N-ethyl-N-cyclohexyl-oleamide This compound was prepared bythe procedure of Example 1, from 14.8 grams (0.12 mole) ofN-ethylcyclohexylamine, 9.2 grams (0.12 mole) of pyridine and 35 grams(0.12 mole) of oleoyl chloride. Analysis of the product,N-ethyl-N-cyclohexyl-oleamide: percent C, 79.26 (theory 79.80); percentH, 12.52 (theory 12.53); percent N, 3.42 (theory 3.58).

EXAMPLE 44 N-isopropyl-N-cyclohexyl-oleamide This compound was preparedby the procedure of Example 1, from 18.8 grams (0.13 mole) ofN-isopropylcyclohexylamine, 40 grams (0.13 mole) of oleoyl chloride and10.5 grams (0.13 mole) of pyridine. Analysis of the product,N-isopropyl-N-cyclohexyloleamide: percent C, 79.98 (theory 79.86);percent H, 12.70 (theory 12.57); percent N, 3.60 (theory 3.45).

EXAMPLE 45 N-methyl-N-cyclooctyl-oleamide This compound was prepared bythe procedure of Example 1, from 19 grams (0.13 mole) ofN-methylcyclooctylamine, 40.5 grams (0.13 mole) of oleoyl chloride and10.7 grams (0.13 mole) of pyridine. Analysis of the product,N-methyl-N-cyclooctyl-oleamide: percent C, 78.67 (theory 80.00); percentH, 12.60 (theory 12.69); percent N, 3.42 (theory 3.46).

EXAMPLE 46 N-methyl-N-cyclododecyl-oleamide This compound was preparedby the procedure of EX- ample 1, from 19 grams (0.10 mole) ofN-methylcyclododecylamine, 31 grams (0.10 mole) of oleoyl chloride, and7.6 grams (0.10 mole) of pyridine. Analysis of the product,N-methyl-N-cyclododecyl-oleamide: percent C, 80.81 (theory 80.69);percent H, 12.91 (theory 12.91); percent N, 3.03 (theory 3.04).

EXAMPLE 47 N-isopropyl-N-benzyl-oleamide This compound was prepared bythe procedure of Example 1, from 19.8 grams (0.12 mole) ofN-benzylisopropylamine, 40 grams (0.13 mole) of oleoyl chloride and 10.5grams (0.13 mole) of pyridine. Analysis of the product,N-isopropyl-N-benzyl-oleamide: percent C, 81.27 (theory 81.22); percentH, 11.61 (theory 11.36); percent N, 3.39 (theory 3.39).

EXAMPLE 48 1 1 EXAMPLE 49 N-methyl-N-tetrahydrofurfuryl-oleamide Thiscompound was prepared by the procedure of Example 1, from 14.8 grams(0.12 mole) of N-methyltetrahydrofurfurylamine, 9.2 grams (0.12 mole) ofpyridine and 35 grams (0.12 mole) of oleoyl chloride. Analysis of theproduct, N-methyl-N-tetrahydrofurfuryl-oleamide: percent C, 75.91(theory 75.87); percent H, 11.83 (theory 12.22); percent N, 3.59 (theory3.69).

EXAMPLE 5O N-methyl-N-Z-acetoxyethyl-oleamide Fifty grams (0.17 mole) ofmethyl oleate was slowly added to a vigorously stirred mixture of 13.4grams (0.18 mole) of N-methylaminoethanol and 2.7 grams (0.12 mole) ofmetallic sodium dissolved in absolute methanol. The reaction was carriedout with continued stirring at 65 to 75 C. and at 60 mm. pressure. Thereaction was complete after all the methyl oleate had been added and theevolution of methanol had ceased. To 24 grams (0.71 moles) of theproduct N-oleoyl-N-methylethanolamine which was isolated from thereaction mixture by the addition of a slight excess of glycolic acidfollowed by extrac tion with hexane, washing and stripping, was added5.8 grams (0.74 mole) of acetyl chloride and 5.6 grams (0.71 mole) ofpyridine. The reaction was carried out in 75 grams of benzene. After thereaction was complete the mixture was filtered, washed successively withdilute hydrochloric acid and water, and finally stripped to remove thebenzene. Analysis of the product N-methyl-N-Z-acetoxyethyl-olea'mide:percent C, 71.25 (theory 72.33); percent H, 11.45 (theory 11.36);percent N, 3.71 (theory EXAMPLE 51 N-ethyl-N-Z-acetoxy-oleamide Thismaterial was prepared by the procedure of Example 50, substitutingN-ethylaminoethanol for N-methylaminoethanol. Analysis of the product,N-ethyl-N-Z-acetoxyethyl-oleamide: percent C, 72.99 (theory 72.83);percent H, 11.39 (theory 11.38); percent N, 3.35 (theory 3.54).

EXAMPLE 52 N-isopropyl-N-Z-acetoxyethyl-oleamide This compound wasprepared by the procedure of Example 50, substitutingN-isopropylaminoethanol for N- methylaminoethanol. Analysis of theproduct, N-isopropyl-N-2-acetoxyethyl-oleamide: percent C, 73.91 (theory73.35); percent H, 11.92 (theory 11.49); percent N, 2.93 (theory 3.42).

EXAMPLE 53 N-butyl-N-Z-acetoxyethyl-olearnide This material was preparedby the procedure of EX- ample 50, substituting N-butylaminoethanol forthe N- methylaminoethanol. The isolated product, N-butyl-N-Z-acetoxyethyl-oleamide, gave the following analysis: percent C, 73.47(theory 73.66); percent H, 11.63 (theory 11.66); percent N, 3.44 (theory3.31).

EXAMPLE 54 N-ethyl-N-3-ethoxypropyl-oleamide This compound was preparedby the procedure of Example 1, from grams (0.19 mole) ofN-(3-ethoxypropyl)ethylamine, 57.2 grams (0.19 mole) of oleoyl chloride,and 15.1 grams (0.19 mole) of pyridine. Analysis of the product,N-ethyl-N-3-ethoxypropyl-oleamide: percent C, 75.96 (theory 75.83);percent H, 12.67 (theory 12.48); percent N, 3.56 (theory 3.54).

12 EXAMPLE 55 N-cyclohexyl-N-Z-acetoxyethyl-oleamide This compound wasprepared by the procedure of Example 50, substitutingN-cyclohexylaminoethyl for N-methylaminoethanol. Analysis of theproduct, N-cyclohexyl N 2 acetoxyethyl-oleamide: percent C, 74.65(theory 74.73); percent H, 11.43 (theory 11.45); percent N, 3.30 (theory3.12).

EXAMPLE 5 6 N-cyclohexyl-N-2-cyanoethyl-oleamide This compound wasprepared by the procedure of Example 1, from 20.5 grams (0.13 mole) ofN-(2-cyanoethyl)cyclohexylamine, 40 grams (0.13 mole) of oleoyl chlorideand 10.2 grams (0.13 mole) of pyridine. Analysis of the product,N-cyclohexyl-N-2-cyanoethyl-oleamide: percent C, 78.08 (theory 77.00);percent H, 11.77 (theory 11.29); percent N, 6.90 (theory 7.19).

EXAMPLE 57 Nbenzyl-N-2-acetoxyethyl-oleamide This compound was preparedby the procedure of Example 50, substituting N-benzylaminoethanol forN-methylaminoethanol. Analysis of the product N-benzyl-N-Z-acetoxyethyl-oleamide: percent C, 75.67 (theory 76.15); percent H,10.27 (theory 10.28); percent N, 2.88 (theory 3.06).

EXAMPLE 58 N,N-bis [2- (3 -carb obutoxypropionyloxy) ethyl] oleamide To37 grams (0.10 mole) of N,N-bis(2-hydroxyethyl) oleamide was addeddropwise with stirring 46 grams (0.22 mole) of3-chloroformylbutylpropionate in the presence of 20 grams (0.25 mole) ofpyridine. After reacting for an additional hour the product wasdissolved in hexane, filtered, washed successively with aqueoushydrochloric acid and water, and dried over anhydrous sodium sulfate.The solvent was removed by stripping under reduced pressure. Analysis ofthe product, N,N-bis[2-(3-carbobutoxypropionyloxy)ethyl1-oleamide:percent C, 67.90 (theory 66.90); percent H, 10.24 (theory 9.90); percentN, 2.08 (theory 2.06).

EXAMPLE 59 N,N-b is [2- (3 -carbohexanoxypropionyloxy) ethyl} oleamideThis compound was prepared by the procedure of Example 58, from 36.9grams (0.10 mole) of N,N-bis(2- hydroxyethyl)oleamide, 48 grams (0.22mole) of 3-chl0- roformylhexylpropionate and 20 grams (0.25 mole) ofpyridine. Analysis of the product,N,N-bis[2-(3-carbohexanoxypropionyloxy)ethyl]oleamide: percent C, 69.05(theory 68.40); percent H, 10.32 (theory 10.19); percent N, 2.06 (theory1.91).

EXAMPLE 60 N,N-di-n-butyl-2- (oleoyloxy) propionamide 153.2 grams (1.19moles) of di-n-butylamine and 70 grams (0.59 mole) of ethyl lactate wererefluxed for 16 hours at a temperature just sutficient to liberate theethanol formed. After the excess dibutylamine had been stripped underreduced pressure, the product N-lactoyldibutylamine was obtained byvacuum distillation, dissolving in ether and percolating through acolumn of activated alumina. The solvent was then removed by strippingunder reduced pressure. To 30 grams (0.15 mole) of the productN-lactoyldibutylamine was added, 11.8 grams (0.15 mole) of pyridine, and48.9 grams (0.16 mole) of oleoyl chloride. The reaction was carried outin ml. of benzene. The reaction product was isolated from this mixtureby filtration, followed by washing with dilute hydrochloric acid andwater, and finally stripped to remove the ben- 13 zene. Analysis of theproduct N,N-di-n-butyl-2-(oleoyloxy)propionamide: percent C, 73.39(theory 74.71); percent H, 11.78 (theory 11.81); percent N, 2.99 (theory3.01).

Portions of the products prepared according to the examples set forthabove were evaluated as primary, solvent-type plasticizers forvinyl-type resins by the following procedures:

1. Incorporating the plasticizer in a vinyl chloride-vinyl acetatecopolymer (Vinylite VYDR) a copolymer consisting of 95% vinyl chlorideand vinyl acetate.

2. Incorporating the plasticizer in a polyvinyl chloride homopolymer(Geon 101).

In either method, the following standard formulation is used, percentbeing by weight: 63.5% homopolymer (or copolymer), 35.0% plasticizer,0.5% stearic acid, and, as stabilizer, 1.0% basic lead carbonate.

The formulation for each sample is then milled, molded, and then testedfor: (a) tensile strength (p.s.i.); (b) 100% modulus (p.s.i.); (c)elongation (percent); (d) brittle point C.); (e) volatility loss inpercent; and, (f) compatibility. Portions of the milled samples weretested for antistatic properties and for thermal stability.

The results of the above tests are then compared with control resultsobtained when a standard plasticizer such as di-2-ethylhexylphthalate(DOP) is used. These results are summarized in Tables I and 11. In TableI, C denotes compatibility and 1 denotes incompatibility as primaryplasticizers in the proportions used. The sample was rated asincompatible if the molded stock showed any evidence of exudation ormigration to the surface during a shelf storage of 30 days.

The antistatic properties of the plasticized resins were determined bythe following procedure: A sheet of the milled plastic composition isstroked ten times in the same direction with unsoiled nylon fabrictautly draped over the bristles of a scrubbing brush and is thencarefully placed so as to fully cover a /2-inch deep Petri dishcontaining a layer of 'finely powdered cigar ashes. Those samplesattracting and holding the greatest quantity of ash have poor antistaticproperties and are given a rating of 4. Conversely those attracting noash have excellent antistatic properties and are rated 0. Those rated 3,2, and 1 are intermediate in antistatic effect. The nylon fabric ischanged after each test. The ratings are reported in Table I.

The relative thermal stabilities of the plasticized compositions weredetermined by the following test procedure: A 3 x 4-inch sheet of themilled plasticized composition, to mils in thickness, is laid on aluminafoil and subjected to a temperature of 176 C. in a forced draft oven forincremental exposure periods of minutes. Every thirty minutes thespecimen is removed from the oven, cooled, and placed on a standardwhite background. The reflectance is then determined by means of aphotoelectric reflectometer (we used Model No. 610 of the PhotovoltCorp.) employing the amber 0, directional reflectance. The loss inreflectance is a measure of degree of discoloration. The results, givenin Table II, show the loss in reflectance expressed as percent oforiginal reflectance of the untreated sample. Compositions retaining thegreatest percentage of their initial reflectance value, i.e., thoseexhibiting the smallest reflectance loss for a given exposure period,have the greatest thermal stability.

The improved thermal stability of the polyvinyl chloride resinplasticized with N,N-n-dibutyl oleamide over that with N,N-dirnethyloleamide is shown more emphatically when a highly efficient but muchmore expensive sta-bilizer formulation is used instead of basic leadcarbonate, as shown by the thermal stability data in Table III for aplastic composition of the following formulation, percent being byweight: 62.7% Vinylite VYDR, 34.6% plasticizer, 0.5% stearic acid, 2%polymeric dibutyl tin mercaptide (Avastab T360), and 0.2%alkylarylphosphite (Avastab CH300).

TABLE I Tensile Elonga- Brittle Volatility A tistrength, modulus, tion,point, loss, Compattati No. Plasticizer p.s.i. p.s.i. percent 0. percentlblllty ratin b 1 N N-di-nropyl-oleamido 2, 600 1, 270 370 61 0. 77 C 0N :N-di-ixfiJropyl-olcamide 2, 960 1, 660 330 -53 2. 49 C 0 3N,N-di-n-bntyl-oleamide 2, 710 1, 470 335 -63 1. 27 C 0 3aN,Ndi-n-butyl-oleamide 2, 640 1, 520 300 59 1.07 C 4 N,N-di-sec-butyl-oleamide- 2, 650 1, 720 320 -58 2. 51 C N,N-isobutyl-oleamide... 2, 730 1, 540 310 55 2. 64 C N,N-di-n-amyloleamide. 2, 680 1, 500 330 -61 0. 67 CN,Ndi-isoarnyl-oleamide- 3, 180 1, 540 340 59 1. 08 C N,Ndi-2-amyl-oleamide 1, 970 1, 780 160 -33 O N ,N-di-n hexyl-oleami d n 2,506 1, 630 280 63 0. 27 C N ,Ndi-n-heptyl-oleam e 1, 460 33 0. 84 C 11N,Ndi-n-octyl-oloamide Would not null I 12 N,N-di-2-ethylhexyl-oleamideWould not null I 13"--- N ,N-di-n-decyl-oleamide Would not null I 14,. N,Ndi-n-butyl-Q-ethylhexan amide 2, 610 1, 180 350 41 10. 21 C 15-..-N,N-di-n-butyl'neodecanamide 2, 980 1, 570 340 27 10. 36 C 16.N,N-di-n-butyl-neotridecau 2, 790 2,100 330 23 9. 66 0 l7N,N-di-n-butyl-p lmitam 2, 730 1, 360 350 47 0. 66 O 18-- N,N-di-n-butyl-stearami d e 2, 540 1, 540 340 37 0. 93 I N,N-di-n-butyl-emcamide. 2, 380 1, 620 250 57 0. 28 C N,N-di-n-butyl-epoxystearami 2, 800 1, 190 360 35 0. 46 C N ,N-din-butyllinoleamide 2, 760 1, 340 350 57 2. 23 I N,N-di-n-butyl-ricinoleamidImmediate bleeding I N,N-di-n-butyl-naphthenarnid 2, 970 1, 610 300 -218. 32 C N,N,N,N-tetra-n-bi(ityl dliaruild )111 b 1 2, 950 2, 180 230 230. 00 C Ethyl 2 2dimeth l-3 di-nuty amino car ony cyeloliutaneace ate.3, 060 1, 460 300 -7 5. 16 C 26.- N,N-diu-butyl amide of cottonseedfatty acids 2, 840 1, 310 400 57 2. 38 I 27. N,N-di-n-l)1utyl amide ofselectively hydrogenated cottonseed 2, 630 1, 420 350 57 1. 11 0 fattyaci s. 28. N,N-di-ri-butyl amide oi rapeseed fatty acids 2, 740 1, 650290 57 0. 39 I 29. N,N-d.i-n-butyl amide of Limnanthes do'ualaaii fattyacids. 2, 560 1, 520 330 53 0.91 C 30..- N,N-di-n-butyl amide of animalacids 2, 600 1, 470 330 51 0. 62 C 31 N,N-di-n-butyl amide of parsleyseed fatty acids 2, 810 1,450 350 57 2. 61 O 32 N methyl-N-propyl-nleamide 2, 510 1, 380 59 2. 29 C 33.- N-methyl-N-n-butyl-oleamide 2, 620 1,250 350 61 1. 38 C 34 N methyl-N-n-amyl-oleamide 2, 540 1, 370 61 1. 46C 35.--" N-methyl-N-n-hexyl-nlearnide 2, 560 1, 290 370 65 1. 65 C 36.Nmethyl-N-n-oetyl-oleamide 2, 700 1, 400 380 63 1. 07 C 37N-methyl-N-n'do decyl-oleamide. 2, 300 1, 590 260 53 0. 92 C 38..."N-methyl-N-allyboleamide 2, 380 1, 130 310 61 C 39.N-n-butyl-Nn-dodecyl-dodecyl-oleamlde- Would not null I) 40..N-n-butyl-N-n-propyloleamide 2, 650 340 390 61 0. 72 C 0 41.-Nn-butyl-N-n-amyl-oleamide 2, 710 1, 540 320 -61 0. 60 C 0 42N-methyl-Ncyclopentyboleamide- 2, 810 1, 500 360 41 0. 74 C 0 43Nethyl-N-cyclohexyl-oleamide 2, 820 1, 460 350 37 0. 68 a 44...Nisopropyl-N-eyelohexyl-oleamice 2, 960 1, 850 310 39 73 loss,Compatpercent ibility Plasticizer Ex. No.

CCCCOCC CCCCO CCC 150 min.

120 min.

90 min.

of copolyr ner resin (V lnylite VYD R). of zero was obtained for each ofthese plasticized resin samples after a very thin film of the specificplasticizer used as plestlcizer had been applied to the surface of theplasticized resin.

Percent loss in reflectance after- 30 min.

min.

I C=compatlble, I=incompatible. b Ratings from (excellent antistaticproperties) to 4 (no antistatic properties) Same as Example 3 usingpolyvinyl chloride homopoly-mer instead 6 A rating TABLE II PlasticlzerEx. No.

664.69LQmL L7 3 333366556645$MH rsseeeeeeeaze 180 min. 210 min.

TABLE III Percent loss in reflectance after- 0 min. min. min. min. min.min.

a Commercial product. b Di-Z-ethylhexyl phthalate.

Plasticlzer S e m R 0 m m mm nY D 0 0 111 mflimmmw m emmmmeee emerge mNNNNNNNN ND u nu Ex. N0.

man

N,N-dimethyl-oleamide 1...-.. N,N-di-n-propyl oleamide.. 3...N,N-d.i-n-butyl-oleamide LEWIS 'GO'ITS, Primary Examiner ETHEL G. LOAssistant Examiner 50 U.S. C1. X.R.

We claim: 1. N-ethyl-N-3-ethoxypropy1-oleamide.

References Cited UNITED STATES PATENTS 3,309,333 3/1967 Mod et a1.26032.6 3,704,257 11/1972 Mod et a1. 260--404.5

